Stain and fouling resistant polyurea and polyurethane coatings

ABSTRACT

Transporters, e.g., ore carriers, vehicles, materials handling equipment, etc. having fluorinated polyurea and fluorinated polyurethane coatings thereon.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 60/882,790, filed Dec. 29, 2006.

FIELD

The present invention relates to polyurea compositions and polyurethanecompositions for forming coatings and coatings formed from suchcompositions. In particular the invention relates to stain and foulingresistant coatings, e.g., for use on rail cars, containers, vehicles,etc.

BACKGROUND

It has been known to use polyurethane compositions and polyureacompositions for forming coatings on substrates for a variety ofpurposes. Such compositions have been applied in a variety of approachesincluding spraying.

Although such coatings have been used in a variety of applications, adeficiency has been the tendency of such coatings to stain and/or foul.Such staining or fouling may be of mere aesthetic concern or may, insome cases, represent an important functional or performance deficiency.

A developing energy source is oil from oil sands and tar sands. Suchsands tend to stick to equipment and vehicles used to move and processthem. As a result, efficiency is reduced as the deposits build up,increasing the weight of moving vehicles, clogging handling chutes, etc.It is common practice today to remove vehicles used in such operationsfrom service for one or two days each week for extensive spray washingto remove the build up of deposits from the vehicle in addition to anextensive solvent wash done on a monthly basis.

An established energy source is coal which is mined in one location andthen shipped to another location via such means as rail car. Whenremoved from the mine, coal commonly contains significant water contentand has a temperature of about 40 to about 50° F. (4 to 10° C.). Duringcool months when the coal is placed in rail cars which are at an ambienttemperature close to or below 32° F. (0° C.), the coal will tend tostick to the surfaces of the rail car. When the rail car is emptiedsignificant quantities of the load remain stuck to the car. As a result,as much as 25% of the potential load carrying capacity of the rail carsmight be lost. Removal is a labor and cost intensive exercise.

A need exists for conveniently applied polyurethane compositions andpolyurea compositions that provide durable, light weight coatings whichexhibit oil-repellency, water-repellency, and stain resistance.

SUMMARY OF INVENTION

The present invention provides novel polyurethane compositions andpolyurea compositions and novel coatings formed therefrom, andtransporters, e.g., carriers, vessels, and vehicles, having suchcoatings thereon.

In brief summary, the compositions of the invention comprise reactiveprecursors for forming a polyurethane or polyurea coating and at leastone fluorochemical fluorochemical compound.

The compositions of the invention can be applied in convenient manner,e.g., spraying, to form films or coatings on substrates. The resultantfilms or coatings can exhibit exceptional physical properties such ashigh hardness, flexibility, abrasion resistance, and chemicalresistance. Durable and light weight, films and coatings of theinvention exhibit oil-repellency, water-repellency, and stainresistance. The invention provides polyurethane and polyurea coatingsthat provide heretofore unattainable resistance to staining and fouling.

DETAILED DESCRIPTION OF INVENTION

Compositions of the invention comprise reactive precursors for formingpolyurethane and/or polyureas and at least one fluorochemical compound.In preferred embodiments, the fluorochemical compound is reactive withone or more of the reactive precursors.

Polyurethanes can be prepared by reacting one or more isocyanates withone or more polyols. Polyureas can be prepared by reacting one or moreisocyanates with one or more amines.

An illustrative class of fluorochemical compounds suitable for useherein include the fluorochemical monoisocyanates disclosed in U.S. Pat.No. 7,081,545 (Klun et al.) which is incorporated herein by reference inits entirety.

Fluorochemical alcohols that are useful in carrying out the inventioninclude those represented by the following formula:C_(n)F_(2n+1)SO₂NCH₃(CH₂)_(m)OHwherein n=2 to 5, and m=2 to 4 (preferably, n=2 to 4; more preferably,n=4). Fluorochemical alcohols that are useful starting compounds includeC₂F₅SO₂NCH₃(CH₂)₂OH, C₂F₅SO₂NCH₃(CH₂)₃OH, C₂F₅SO₂NCH₃(CH₂)₄OH,C₃F₇SO₂NCH₃(CH₂)₂OH, C₃F₇SO₂NCH₃(CH₂)₃OH, C₃F₇SO₂NCH₃(CH₂)₄OH,C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₃OH, C₄F₉SO₂NCH₃(CH₂)₄OH,C₅F₁₁SO₂NCH₃(CH₂)₂OH, C₅F₁₁SO₂NCH₃(CH₂)₃OH, C₅F₁₁SO₂NCH₃(CH₂)₄OH, andmixtures thereof. Preferred fluorochemical alcohols include, forexample, C₂F₅SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₄OH,and mixtures thereof. More preferred fluorochemical alcohols include,for example, C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₄OH, and mixturesthereof. A most preferred fluorochemical alcohol is C₄F₉SO₂NCH₃(CH₂)₂OH.Useful fluorochemical alcohols can be purchased from 3M (St. Paul,Minn.), or can be prepared essentially as described in U.S. Pat. Nos.2,803,656 (Ahlbrecht et al.) and 6,664,345 (Savu et al.).

The above-described fluorochemical alcohols can be reacted with4,4′-diphenylmethane diisocyanate in a solvent to form the correspondingmonoisocyanates. 4,4′-Diphenylmethane diisocyanate is commonly known as“methylene diisocyanate” or “MDI”. In its pure form, MDI is commerciallyavailable as ISONATE™ 125M from the Dow Chemical Company (Midland,Mich.), and as MONDUR™ M from Bayer Polymers (Pittsburgh, Pa.).

The process of the invention can be carried out with a molar ratio offluorochemical alcohol:MDI from about 1:1 to about 1:2.5. Preferably,the molar ratio of fluorochemical alcohol:MDI is from about 1:1 to about1:2. More preferably, the molar ratio is from about 1:1.1 to about1:1.5.

The process of the invention can be carried out in a solvent in whichthe resulting monoisocyanate is not soluble (that is, the solvent is onein which the monoisocyanate partitions out of so that it no longerparticipates in the reaction). Preferably, the solvent is a nonpolarsolvent. More preferably, it is a nonpolar non-aromatic hydrocarbon orhalogenated solvent.

Representative examples of useful solvents include cyclohexane,n-heptane, hexanes, n-hexane, pentane, n-decane, i-octane, octane,methyl nonafluoroisobutyl ether, methyl nonafluorobutyl ether, petroleumether, and the like, and mixtures thereof. A mixture of methylnonafluoroisobutyl ether and methyl nonafluorobutyl ether is availableas HFE-7100 NOVEC™ Engineered Fluid from 3M. Preferred solvents include,for example, methyl nonafluoroisobutyl ether, methyl nonafluorobutylether, petroleum ether, n-heptane, and the like.

Preferably, the solvent has a Hildebrand solubility parameter (6) ofless than about 8.3 (cal/cm³)^(1/2) (about 17 MPa^(1/2)) and a hydrogenbonding index of less than about 4. The Hildebrand solubility parameteris a numerical value that indicates the relative solvency behavior of aspecific solvent. It is derived from the cohesive energy density (c) ofthe solvent, which in turn is derived from the heat of vaporization:$\begin{matrix}{{\delta\quad\overset{\_}{c}} = \left\lbrack \frac{{\Delta\quad H} - {RT}}{V_{m}} \right\rbrack^{\frac{1}{2}}} & (2)\end{matrix}$

wherein:

ΔH=heat of vaporization,

R=gas constant,

T=temperature, and

Vm=molar volume

For example, n-heptane has a Hildebrand solubility index of about 7.4(cal/cm³)^(1/2) (about 15 MPa^(1/2)), and water has a Hildebrandsolubility index of about 23.4 (cal/cm³)^(1/2) (about 48 MPa^(1/2))(Principles of Polymer Systems, 2^(nd) edition, McGraw-Hill BookCompany, New York (1982)).

The hydrogen bonding index is a numerical value that indicates thestrength of the hydrogen bonding that occurs in a solvent. Hydrogenbonding values range from −18 to +15. For example, n-heptane has ahydrogen bonding value of about 2.2, and water has a hydrogen bondingvalue of about 16.2 (Principles of Polymer Systems, 2^(nd) edition,McGraw-Hill Book Company, New York (1982)).

The reaction can be carried out by combining the fluorochemical alcoholand MDI in the solvent. Preferably, the fluorochemical alcohol is addedto MDI, which is in the solvent, over time. Optionally, thefluorochemical alcohol can first be dissolved in a solvent such as, forexample, toluene, and then added to the MDI in solution. Preferably, thereaction mixture is agitated. The reaction can generally be carried outat a temperature between about 25° C. and about 70° C. (preferably,between about 25° C. and about 50° C.).

Optionally, the reaction can be carried out in the presence of acatalyst. Useful catalysts include bases (for example, tertiary amines,alkoxides, and carboxylates), metal salts and chelates, organometalliccompounds, acids, and urethanes. Preferably, the catalyst is anorganotin compound (for example, dibutyltin dilaurate (DBTDL)) or atertiary amine (for example, diazobicyclo[2.2.2]octane (DABCO)), or acombination thereof. More preferably, the catalyst is DBTDL.

After the reaction is carried out, the reaction product can be filteredout and dried. The reaction product typically comprises greater thanabout 85% of the desired fluorochemical monoisocyanate (preferably,greater than about 90%; more preferably, greater than about 95%).

Fluorochemical monoisocyanates that can be prepared using the process ofthe invention can be represented by the following formula:

wherein n=2 to 5, and m=2 to 4.

Preferred fluorochemical monoisocyanates that can be prepared using theprocess of the invention include, for example:

More preferred fluorochemical monoisocyanates prepared using the processof the invention include, for example:

Fluorochemical monoisocyanates prepared using the process of theinvention can be useful starting compounds in processes for preparingfluorinated acrylic polymers with water- and oil-repellency properties.

For example, fluorochemical monoisocyanates prepared using the processof the invention can be reacted with active hydrogen-containingcompounds, materials, or surfaces bearing hydroxyl, primary or secondaryamines, or thiol groups. The monomer produced by reacting afluorochemical monoisocyanate prepared by the process of the inventionwith a hydroxy alkyl acrylate such as hydroxy ethyl acrylate, forexample, can be polymerized (alone or with comonomers) to providepolymers that have useful water- and oil-repellency properties.

In some preferred embodiments, compositions of the invention willfurther comprise filler materials such as glass microspheres, glassbubbles, ceramic microspheres, or other particles.

The surprising combination of properties exhibited by films and coatingsof the invention makes them advantageously suited for a variety ofapplications.

For example, coatings of the invention can be used as coatings on motorvehicle bodies, undercarriages, truck beds, carriers and vessels usedfor transporting materials, etc. The coatings exhibit good adhesion tometal substrates coupled with oil-repellency, water-repellency, andstain resistance.

An illustrative application of the compositions and coatings of theinvention is on equipment and vehicles used in mining operations, e.g.,for oil sands and tar sands. Despite the tendency of such sands to stickto equipment and vehicles used to move and process them, use of coatingsof the invention will reduce the maintenance time required to cleanconventional equipment and vehicles, thereby reducing downtime andincreasing efficiency of operations. With the improved releaseproperties achieved in accordance with the present invention, suchcostly down-time operations can be reduced, resulting in greaterproductivity, lower operating costs, etc. Similarly, railcars canoutfitted with coatings of the invention to reduce the build up of coal,resulting in increased transportation efficiency.

The invention may be used to advantageous effect in a variety ofapplications where durable, abrasion-resistant coatings exhibitingoil-repellency, water-repellency, and stain resistance and desired.

Coatings of the invention exhibit good adhesion to metal substrates.

Coatings of the invention preferably contain glass microspheres and orbubbles to impart improved insulative properties (e.g., thermalinsulation, noise dampening, vibration, etc.), reduce effective weightof the coating. In some embodiments, coatings of the invention are madein combination with open celled, foamed construction.

Coatings of invention can be made with superior abrasion resistance andhardness.

Compositions of invention can be applied by any of a variety oftechniques. In some embodiments, compositions of the invention can beapplied by such convenient techniques as spraying.

Coatings of the invention can applied over other, less durableinsulation materials to provide optimized, composite properties. Forexample, the present invention may be used to provide a polyureainsulation coating sprayed over other insulation materials such aspolystyrene or polyurethane open cell foam insulation, or otherinsulative material.

Films and coatings of the invention may be used in conjunction withother materials and layers to make multilayer composite constructionsoffering desired performance. For example, Compositions of the inventioncan be coated over blast and tear resistant films to impart improvedblast and/or projectile resistance.

The combination of convenient application and high performance providedby compositions and coatings of the invention makes them well suited fora wide variety of applications. Some examples include protectivecoatings to protect the cab, passenger compartment, load area, or otherchambers of vehicles including aircraft, watercraft and land vehicles.For example, the invention provides advantageous results on wheeled andtracked vehicles, e.g., trucks, HUMVEEs, tanks, etc., airplanes, spacevehicles, helicopters, boats and other enclosed cockpit vehicles, fromheat from engines or ambient sources. Other examples include protectivecoatings on equipment and vehicles or vehicle components that are usedin extreme environments, e.g., trucks, tanks, airplanes, space vehicles,helicopters, boats, pipes, bridges, off-shore oil platforms, and othermetallic substrates used in extreme environments or washed with bleachand other corrosive materials to provide corrosion resistance for themetal substrates. The invention can be used on a variety of materialshandling equipment including wheelbarrows, pipelines, sluices, etc.

EXAMPLES

The invention will be further explained with the following illustrativeexamples.

Test Methods

Dynamic Contact Angle Measurement

Advancing and receding contact angles on the polyurea samples weremeasured using a CAHN Dynamic Contact Angle Analyzer, Model DCA 322 (aWilhelmy balance apparatus equipped with a computer for control and dataprocessing, commercially available from ATI, Madison, Wis.). Water wasused as the probe liquid.

Static Contact Angle Measurement

The treated substrates were tested for their contact angles versus waterusing an Olympus TGHM goniometer (Olympus Corp, Pompano Beach, Fla.).Contact angles were measured at least 24 hrs after cure. The values arethe mean values of 4 measurements and are reported in degrees. Theminimum measurable value for a contact angle was 20. A value less than20 means that the liquid spreads on the surface.

Thermal Conductivity Test Method 1

Thermal conductivity was measured using a Model 2021 ThermalConductivity Apparatus (available from Anter Corporation, Pittsburgh,Pa.) following ASTM E 1530 (Test Method for Evaluating the Resistance toThermal Transmission of Thin Specimens of Materials by the Guarded FlowMeter Technique).

Thermal Conductivity Test Method 2—Hot Face vs. Cold Face

A 4 inch×6 inch (10.16 cm×15.24 cm) rectangular hole was cut in the topof a lab furnace (Econo-Kiln, Model K 14, L & L Manufacturing Co., TwinOaks, Pa.; maximum temperature of 1832° F. (1000° C.)). The sample to betested was placed over the rectangular hole in the furnace such that theedges of the sample fully overlapped on all sides of the opening. Twothermocouples (Type K Thermocouple Thermometer, Model 650, OmegaEngineering, Inc., Stamford, Conn.) were placed in the center of thesample and held in contact with a foil tape. One thermocouple measuresthe external face temperature (T_(Outside)) of the sample (that portionoutside the oven) and one thermocouple measures the internal facetemperature T_(Inside) of the sample (that portion inside the furnace).The furnace oven was turned on and the I_(Inside) of the sample wasadjusted to 200° F. (93.3° C.). After several minutes, the T_(Outside)was recorded. Additionally, Model ThermaCAM™ P65 infrared camera,available from Flir Systems Inc., Portland, Oreg., was used to analyzethe temperature of the external face surface of the sample.

Comparative Example 1

A two component polyurea (Part A and Part B) was formulated as follows.Part A contained hexamethylene diisocyanate (85.2% by weight, obtainedfrom Rhodia, Inc., Cranbury, N.J., under the trade designation“TOLONATE™ HDT LV2”), glass microspheres (13.5% by weight, obtained from3M Company under the trade designation “3M™ GLASS MICROSPHERES K37”) anda modified polyurea (1.3% by weight, obtained from BYK Chemie, Wesel,Germany, under the trade designation “BYK™ 410”). Part B containeddiethyltoluenediamine (32.4% by weight, obtained from AlbemarleCorporation, Bayport, Tex., under the trade designation “ETHACURE™100”), polyoxypropylenediamine (39.6% by weight, obtained from HuntsmanCorporation, Salt Lake City, Utah under the trade designation“JEFFAMINE™ D-2000”), an aromatic secondary diamine (6.5% by weight,obtained from UOP, A Honeywell Company, Tonawanda, N.Y., under the tradedesignation “UNILINK™ 4200”), a trifunctional amine (2.4% by weight,obtained from Huntsman Corporation under the trade designation“JEFFAMINE™ T-5000”), glass microspheres (18.2% by weight, obtained from3M Company under the trade designation “3M™ GLASS MICROSPHERES K37”), amodified polyurea (0.8% by weight, obtained from BYK Chemie, under thetrade designation “BYK™ 410”) and a liquid organic pigment to producethe desired color (0.1%).

Parts A and B were sprayed from a plural component proportioning sprayer(obtained from Graco, Minneapolis, Minn., under the trade designation“REACTOR H-XP2” using a “FUSION MP” spray gun with nozzles. Each part (Aand B) was kept separate until they exited the spray gun. The twocomponents, A and B, were stirred, in separate pots, in the spray unitand maintained at a temperature of 160° F. (71° C.) during the sprayprocess. The materials (Parts A and B) were sprayed on to a cold rollsteel panel that was previously sprayed with a release agent (fromSierra Paint Co., Minnetonka, Minn., under the trade designation “TK-709UR”) and also waxed paper. The formulation cured within about 20seconds. After a period of time the sprayed panels were peeled from themetal substrate and waxed paper and tested as described above. Thecontact angle data is listed in Table 1. Thermal conductivity data islisted in Table 2.

Example 1

A two component polyurea (Part A and Part B) was formulated as follows.Part A contained hexamethylene diisocyanate (85.2% by weight, obtainedfrom Rhodia, Inc., Cranbury, N.J., under the trade designation“TOLONATE™ HDT LV2”), glass microspheres (13.5% by weight, obtained from3M Company under the trade designation “3M™ GLASS MICROSPHERES K37”) anda modified polyurea (1.3% by weight, obtained from BYK Chemie, Wesel,Germany, under the trade designation “BYK™ 410”). Part B containeddiethyltoluenediamine (31.6% by weight, obtained from AlbemarleCorporation, Bayport, Tex., under the trade designation “ETHACURE 100”),polyoxypropylenediamine (38.7% by weight, obtained from HuntsmanCorporation, Salt Lake City, Utah, under the trade designation“JEFFAMINE™ D-2000”), an aromatic secondary diamine (6.3% by weight,obtained from UOP, A Honeywell Company, Tonawanda, N.Y. under the tradedesignation “UNILINK™ 4200”), a trifunctional amine (2.4% by weight,obtained from Huntsman Corporation under the trade designation“JEFFAMINE™ T-5000”), glass microspheres (17.8% by weight, obtained from3M Company under the trade designation “3M™ GLASS MICROSPHERES K37”), amodified polyurea (0.7% by weight, obtained from BYK Chemie, under thetrade designation “BYK™ 410”), deionized water (2.4% by weight) and aliquid organic pigment to produce the desired color (0.1%).

Parts A and B were sprayed from a plural component proportioning sprayer(obtained from Graco, Minneapolis, Minn., under the trade designation“REACTOR H-XP2” using a “FUSION MP” spray gun with nozzles. Each part (Aand B) was kept separate until they exited the spray gun. The twocomponents, A and B, were stirred, in separate pots, in the spray unitand maintained at a temperature of 160° F. (71° C.) during the sprayprocess. The materials (Parts A and B) were sprayed on to a cold rollsteel panel that was previously sprayed with a release agent (fromSierra Paint Co., Minnetonka, Minn., under the trade designation “TK-709UR”) and also waxed paper. The formulation cured within about 20seconds. After a period of time the sprayed panels were peeled from themetal substrate and waxed paper. The contact angle data is listed inTable 1. Thermal conductivity data is listed in Table 2.

Example 2

A two component polyurea (Part A and Part B) was formulated as follows.Part A contained hexamethylene diisocyanate (84.4% by weight, obtainedfrom Rhodia, Inc., Cranbury, N.J., under the trade designation“TOLONATE™ HDT LV2”), glass microspheres (12.3% by weight, obtained from3M Company under the trade designation “3M™ GLASS MICROSPHERES K37”), amodified polyurea (1.3% by weight, obtained from BYK Chemie, Wesel,Germany, under the trade designation “BYK™ 410”) and a fluorochemicalurethane (2% by weight, obtained from 3M Company under the tradedesignation “SRC-220”. Part B contained diethyltoluenediamine (32.4% byweight, obtained from Albemarle Corporation, Bayport, Tex., under thetrade designation “ETHACURE™ 100”), polyoxypropylenediamine (39.6% byweight, obtained from Huntsman Corporation, Salt Lake City, Utah underthe trade designation “JEFFAMINE™ D-2000”), an aromatic secondarydiamine (6.5% by weight, obtained from UOP, A Honeywell Company,Tonawanda, N.Y. under the trade designation “UNILINK™ 4200”), atrifunctional amine (2.4% by weight, obtained from Huntsman Corporationunder the trade designation “JEFFAMINE™ T-5000”), glass microspheres(18.2% by weight, obtained from 3M Company under the trade designation“3M™ GLASS MICROSPHERES K37”), a modified polyurea (0.8% by weight,obtained from BYK Chemie, under the trade designation “BYK™ 410”), and aliquid organic pigment to produce the desired color (0.1%).

Parts A and B were sprayed from a plural component proportioning sprayer(obtained from Graco, Minneapolis, Minn., under the trade designation“REACTOR H-XP2” using a “FUSION MP” spray gun with nozzles. Each part (Aand B) was kept separate until they exited the spray gun. The twocomponents, A and B, were stirred, in separate pots, in the spray unitand maintained at a temperature of 160° F. (71° C.) during the sprayprocess. The materials (Parts A and B) were sprayed on to a cold rollsteel panel that was previously sprayed with a release agent (fromSierra Paint Co., Minnetonka, Minn., under the trade designation “TK-709UR”) and also waxed paper. The formulation cured within about 20seconds. After a period of time the sprayed panels were peeled from themetal substrate and waxed paper and tested as described above. The datais listed in Table 1.

Example 3

A two component polyurea (Part A and Part B) was formulated as follows.Part A contained hexamethylene diisocyanate (76.8% by weight, obtainedfrom Rhodia, Inc., Cranbury, N.J., under the trade designation“TOLONATE™ HDT LV2”), glass microspheres (12.2% by weight, obtained from3M Company under the trade designation “3M™ GLASS MICROSPHERES K37”), amodified polyurea (1.0% by weight, obtained from BYK Chemie, Wesel,Germany, under the trade designation “BYK 410”) and a fluorochemicalurethane (10% by weight, obtained from 3M Company under the tradedesignation “SRC-220”. Part B contained diethyltoluenediamine (32.4% byweight, obtained from Albemarle Corporation, Bayport, Tex., under thetrade designation “ETHACURE™ 100”), polyoxypropylenediamine (39.6% byweight, obtained from Huntsman Corporation, Salt Lake City, Utah underthe trade designation “JEFFAMINE™ D-2000”), an aromatic secondarydiamine (6.5% by weight, obtained from UOP, A Honeywell Company,Tonawanda, N.Y., under the trade designation “UNILINK™ 4200”), atrifunctional amine (2.4% by weight, obtained from Huntsman Corporationunder the trade designation “JEFFAMINE™ T-5000”), glass microspheres(18.2% by weight, obtained from 3M Company under the trade designation“3M™ GLASS MICROSPHERES K37”), a modified polyurea (0.8% by weight,obtained from BYK Chemie, under the trade designation “BYK™ 410”), and aliquid organic pigment to produce the desired color (0.1%).

Parts A and B were sprayed from a plural component proportioning sprayer(obtained from Graco, Minneapolis, Minn., under the trade designation“REACTOR H-XP2” using a “FUSION MP” spray gun with nozzles. Each part (Aand B) was kept separate until they exited the spray gun. The twocomponents, A and B, were stirred, in separate pots, in the spray unitand maintained at a temperature of 160° F. (71° C.) during the sprayprocess. The materials (Parts A and B) were sprayed on to a cold rollsteel panel that was previously sprayed with a release agent (fromSierra Paint Co., Minnetonka, Minn., under the trade designation “TK-709UR”) and also waxed paper. The formulation cured within about 20seconds. After a period of time the sprayed panels were peeled from themetal substrate and waxed paper and tested as described above. The datais listed in Table 1.

Example 4

A two component polyurea (Part A and Part B) was formulated as follows.Part A contained hexamethylene diisocyanate (81.8% by weight, obtainedfrom Rhodia, Inc., Cranbury, N.J., under the trade designation“TOLONATE™ HDT LV2”), glass microspheres (13.0% by weight, obtained from3M Company under the trade designation “3M™ GLASS MICROSPHERES K37”), amodified polyurea (1.2% by weight, obtained from BYK Chemie, Wesel,Germany, under the trade designation “BYK™ 410”) and a fluorochemicalmonoisocyanate (4% by weight, as prepared in U.S. Pat. No. 7,081,545(Klun et al.) Example 5, which is incorporated by reference to theextent that it is not inconsistent with the present disclosure). Part Bcontained diethyltoluenediamine (32.4% by weight, obtained fromAlbemarle Corporation, Bayport, Tex., under the trade designation“ETHACURE™ 100”), polyoxypropylenediamine (39.6% by weight, obtainedfrom Huntsman Corporation, Salt Lake City, Utah under the tradedesignation “JEFFAMINE™ D-2000”), an aromatic secondary diamine (6.5% byweight, obtained from UOP, A Honeywell Company, Tonawanda, N.Y., underthe trade designation “UNILINK™ 4200”), a trifunctional amine (2.4% byweight, obtained from Huntsman Corporation under the trade designation“JEFFAMINE™ T-5000”), glass microspheres (18.2% by weight, obtained from3M Company under the trade designation “3M™ GLASS MICROSPHERES K37”), amodified polyurea (0.8% by weight, obtained from BYK Chemie, under thetrade designation “BYK™ 410”), and a liquid organic pigment to producethe desired color (0.1%).

Parts A and B were sprayed from a plural component proportioning sprayer(obtained from Graco, Minneapolis, Minn., under the trade designation“REACTOR H-XP2” using a “FUSION MP” spray gun with nozzles. Each part (Aand B) was kept separate until they exited the spray gun. The twocomponents, A and B, were stirred, in separate pots, in the spray unitand maintained at a temperature of 160° F. (71° C.) during the sprayprocess. The materials (Parts A and B) were sprayed on to a cold rollsteel panel that was previously sprayed with a release agent (fromSierra Paint Co., Minnetonka, Minn., under the trade designation “TK-709UR”) and also waxed paper. The formulation cured within about 20seconds. After a period of time the sprayed panels were peeled from themetal substrate and waxed paper and tested as described above. The datais listed in Table 1. TABLE 1 Static Contact Angle H2O Dynamic AdvancingSprayed Contact Angle (H₂O) Dynamic Receding Contact Sprayed On SprayedOn Angle (H₂O) On Waxed Sprayed Waxed Sprayed On Sprayed On Steel PaperOn Steel Paper Steel Waxed Paper Comparative 73.1 65 78.2 72.2 42.5 45.6Example 1 Example 2 76.8 65.8 77.9 77.4 48.0 46.8 Example 3 91.2 97.9 99100 33.1 32 Example 4 90 81.5 79.5 74.8 58.0 49.3

TABLE 2 Test Method Comparative Example 1 Example 1 Thermal 250° F./115°F. 250° F./104° F. Conductivity Test Method 2- Hot Face vs. Cold FaceThermal K = 0.1 W/mK @ 58° C. K = 0.07 W/mK @ 58° C. Conductivity TestMethod 1

Various modifications and alterations to this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention. It should be understood that thisinvention is not intended to be unduly limited by the illustrativeembodiments and examples set forth herein and that such examples andembodiments are presented by way of example only with the scope of theinvention intended to be limited only by the claims set forth herein asfollows.

1. A transporter having a coating on at least a portion of the surfacethereof, said coating selected from the group consisting of polyureas,polyurethanes, and combinations thereon which are the reaction productsof precursors including at least one fluorochemical compound.
 2. Thetransporter of claim 1 wherein said transporter is selected from thegroup consisting of rail cars, trucks, automobiles, wheelbarrows, carts,carriers, conveyor belts, tanks, tankers, aircraft, watercraft,pipelines, and sluices.
 3. The transporter of claim 1 wherein saidfluorochemical compounds is a fluorinated isocyanate.
 4. The transporterof claim 3 wherein said fluorinated isocyanate is a fluorinatedmonoisocyanate.